Sluggish sulfur redox kinetics remain a critical bottleneck in the advancement of high-performance lithiumsulfur batteries(LSBs).Single-atom catalysts(SACs)offer a promising solution to this limitation,particularly wh...Sluggish sulfur redox kinetics remain a critical bottleneck in the advancement of high-performance lithiumsulfur batteries(LSBs).Single-atom catalysts(SACs)offer a promising solution to this limitation,particularly when their coordination structures are carefully engineered.Here,we develop a chromium-based SAC featuring a unique undercoordinated CrN_(3) configuration to boost sulfur electrochemistry.Compared with conventional CrN_(4),the CrN_(3) motif lowers 3d orbital occupancy and meanwhile activates the in-plane hybridizations with S 3p orbitals upon interaction with polysulfides,contributing to moderate adsorption strength and reduced energy barriers for bidirectional sulfur conversions.Additionally,the integration of the two-dimensional(2D)porous framework ensures abundant electrochemically active surfaces and efficiently exposed active sites.As a result,CrN_(3)-based cells demonstrate fast and durable sulfur redox reactions,enabling an ultralow capacity decay of 0.0075%per cycle over 1000 cycles and a high-rate capability of 651.9 mAh·g^(-1)at 5 C.The CrN_(3) catalyst retains robust catalytic efficiency under demanding conditions,delivering a high areal capacity of 5.53 mAh·cm^(-2) at high sulfur loading and lean electrolyte.This work establishes a compelling paradigm of SAC coordination engineering for designing advanced sulfur electrocatalysts for next-generation LSBs.展开更多
The hybridization gap in strained-layer InAs/In_(x)Ga_(1−x) Sb quantum spin Hall insulators(QSHIs)is significantly enhanced compared to binary InAs/GaSb QSHI structures,where the typical indium composition,x,ranges be...The hybridization gap in strained-layer InAs/In_(x)Ga_(1−x) Sb quantum spin Hall insulators(QSHIs)is significantly enhanced compared to binary InAs/GaSb QSHI structures,where the typical indium composition,x,ranges between 0.2 and 0.4.This enhancement prompts a critical question:to what extent can quantum wells(QWs)be strained while still preserving the fundamental QSHI phase?In this study,we demonstrate the controlled molecular beam epitaxial growth of highly strained-layer QWs with an indium composition of x=0.5.These structures possess a substantial compressive strain within the In_(0.5)Ga_(0.5)Sb QW.Detailed crystal structure analyses confirm the exceptional quality of the resulting epitaxial films,indicating coherent lattice structures and the absence of visible dislocations.Transport measurements further reveal that the QSHI phase in InAs/In_(0.5)Ga_(0.5)Sb QWs is robust and protected by time-reversal symmetry.Notably,the edge states in these systems exhibit giant magnetoresistance when subjected to a modest perpendicular magnetic field.This behavior is in agreement with the𝑍2 topological property predicted by the Bernevig–Hughes–Zhang model,confirming the preservation of topologically protected edge transport in the presence of enhanced bulk strain.展开更多
The hybridization between oxygen 2p and transition-metal 3d states largely determines the electronic structure near the Fermi level and related functionalities of transition-metal oxides(TMOs).Considerable efforts hav...The hybridization between oxygen 2p and transition-metal 3d states largely determines the electronic structure near the Fermi level and related functionalities of transition-metal oxides(TMOs).Considerable efforts have been made to manipulate the p-d hybridization in TMOs by tailoring the spatial orbital overlap via structural engineering.Here,we demonstrate enhanced p-d hybridization in Ba^(2+)-doped LaNiO_(3)epitaxial films by simultaneously modifying both the spatial and energetic overlaps between the O-2p and Ni-3d orbitals.Combining x-ray absorption spectroscopy and firstprinciples calculations,we reveal that the enhanced hybridization stems from the synergistic effects of a reduced chargetransfer energy due to hole injection and an increased spatial orbital overlap due to straightening of Ni-O-Ni bonds.We further show that the enhanced p-d hybridization can be utilized to promote the oxygen evolution activity of LaNiO_(3).This work sheds new insights into the fine-tuning of the electronic structures of TMOs for enhanced functionalities.展开更多
Introduction Early cancer detection represents a critical evolution in healthcare,addressing a significant pain point in cancer treatment:the tendency for diagnoses to occur at advanced stages.Traditionally,many cance...Introduction Early cancer detection represents a critical evolution in healthcare,addressing a significant pain point in cancer treatment:the tendency for diagnoses to occur at advanced stages.Traditionally,many cancers are not identified until they have progressed to late stages,where treatment options become limited,less effective,and more costly.This late detection results in poorer prognoses,higher mortality rates,and increased healthcare costs.Without early detection tools like Fluorescence In Situ Hybridization(FISH),these challenges persist,leaving patients with fewer opportunities for successful outcomes.展开更多
The biological species concept defines species as groups of actually or potentially interbreeding natural populations that are reproductively isolated from other such groups(Mayr,1942).Reproductive isolation,whether p...The biological species concept defines species as groups of actually or potentially interbreeding natural populations that are reproductively isolated from other such groups(Mayr,1942).Reproductive isolation,whether prezygotic or postzygotic,plays a central role in maintaining species boundaries.However,hybridization between closely related taxa can challenge these boundaries and provide insight into speciation,gene flow,and evolutionary processes(Coyne and Orr,2004).展开更多
Photocatalytic hydrogen(H_(2))production using solar energy is a cutting-edge green technology that holds great potential for addressing the urgent fuel and environmental crises[1–3].To achieve high-efficiency H_(2) ...Photocatalytic hydrogen(H_(2))production using solar energy is a cutting-edge green technology that holds great potential for addressing the urgent fuel and environmental crises[1–3].To achieve high-efficiency H_(2) production,cocatalyst modification is commonly employed to provide active sites for the hydrogen evolution reaction(HER)[4,5].In this context,the kinetics of hydrogen adsorption and desorption at these active sites play a crucial role in enhancing overall photocatalytic H_(2) production efficiency.However,the H adsorption/desorption kinetics often exhibit a trade-off,presenting a significant challenge in achieving an optimal equilibrium between Hads and Hdes in many cocatalyst systems.Therefore,fine-tuning the active sites to optimize the H_(2) evolution kinetics is essential for improving photocatalytic activity[6].展开更多
Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.H...Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.Herein,we find that oxygen vacancies can significantly boost the capacity,electrochemical kinetics,and structure stability of LDHs.The corresponding structure-performance relationship and energy storage mechanism are elaborated through exhaustive in/ex-situ experimental characterizations and density functional theory(DFT)calculations.Specially,in-situ Raman and DFT calculations reveal that oxygen vacancies elevate orbital energy of O 2p and electron density of O atoms,thereby enhancing the orbital hybridization of O 2p with Ni/Co 3d.This facilitates electron transfer between O and adjacent Ni/Co atoms and improves the covalency of Ni–O and Co–O bonds,which activates Ni/Co atoms to release more capacity and stabilizes the Ov-NiCo-LDH structure.Moreover,the distribution of relaxation times(DRT)and molecular dynamics(MD)simulations disclose that the enhanced d-p orbital hybridization optimizes the electronic structure of Ov-NiCo-LDH,which distinctly reduces the diffusion energy barriers of Mg^(2+)and improves the charge transfer kinetics of Ov-NiCo-LDH.Consequently,the assembled Ov-NiCo-LDH//active carbon(AC)and Ov-NiCo-LDH//perylenediimide(PTCDI)AMIBs can both deliver high specific discharge capacity(182.7 and 59.4 mAh g^(−1)at 0.5 A g^(−1),respectively)and long-term cycling stability(85.4%and 89.0%of capacity retentions after 2500 and 2400 cycles at 1.0 A g^(−1),respectively).In addition,the practical prospects for Ov-NiCo-LDH-based AMIBs have been demonstrated in different application scenarios.This work not only provides an effective strategy for obtaining high-performance cathodes of AMIBs,but also fundamentally elucidates the inherent mechanisms.展开更多
Defect engineering significantly enhances electrocatalytic performance by modulating electronic structures and interfacial coordination,yet the dynamic correlation between defect evolution and catalytic activity durin...Defect engineering significantly enhances electrocatalytic performance by modulating electronic structures and interfacial coordination,yet the dynamic correlation between defect evolution and catalytic activity during reactions remains unclear.Herein,density functional theory(DFT)calculations first reveal the modulation of sulfur vacancy concentrations on Co_(9)S_(8)electronic structures,predicting that optimized vacancy concentrations enable highly efficient electrocatalytic water splitting.Experimentally fabricated Co_(9)S_(8)with appropriate sulfur vacancies exhibits superior bifunctional activity(HER:164 mV@_(η10);OER:297 mV@_(η100)).The MCS-assembled overall water splitting system demonstrates stable operation at 1.57 V(10 mA cm^(−2))for over 60 h.Experimental studies illustrate that sulfur vacancies preferentially adsorb OH^(−)during reactions,inducing the formation of CoOOH active phases.DFT analysis further indicates that OH^(−)adsorption weakens d-p orbital hybridization,optimizing hydrogen/oxygen intermediate adsorption energy barriers and ultimately enhancing catalytic performance.This work establishes novel paradigms for systematic development of catalysts through synergistic analysis of defect dynamics,electronic structures and catalytic performance.展开更多
Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains un...Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains unclear.Additionally,the modulation of reactive oxygen species in Fenton-like reactions remains challenging.Herein,a novel strategy is reported for the rational design of highly loaded Co ASACs(CoN_(1)C_(2)/C_(2)N)immobilized on three-dimensional flower-like C_(2)N using an in situ-generated carbon defect method.In particular,the asymmetrically tricoordinated CoN_(1)C_(2)/C_(2)N exhibited excellent catalytic activity for sulfachloropyridazine degradation,with a turnover frequency of 36.8 min^(–1).Experimental results and theoretical calculations revealed that the electron spin state of the Co-active sites was transferred from the low-spin configuration(t_(2g)^(6)e_(g)^(1))to the high-spin configuration(t_(2g)^(5)e_(g)^(2))owing to asymmetric coordination.The high-spin Co 3d orbital in CoN_(1)C_(2)/C_(2)N possessed more unpaired electrons and therefore,had a strong ability to gain electrons from the O 2p orbitals of HSO_(5)^(–),boosting d-p orbital hybridization.More importantly,the spin-electron filling in theσ^(*)orbital of high-spin Co 3d−O 2p accelerated the desorption of^(*)SO_(5)•^(−),which acted as a rate-limiting step in the reaction,thus facilitating more^(1)O_(2)generation.This study provides an innovative synthetic route for practical ASACs and clarifies the critical relationship between structure and spin state,paving the way for advancements in environmental remediation and energy conversion applications.展开更多
Hybridization is a driving force in ecological transitions and speciation,yet direct evidence linking it to adaptive differentiation in natural systems remains limited.This study evaluates the role of hybridization in...Hybridization is a driving force in ecological transitions and speciation,yet direct evidence linking it to adaptive differentiation in natural systems remains limited.This study evaluates the role of hybridization in the speciation of Pinus densata,a keystone forest species on the southeastern Tibetan Plateau.By creating artificialinterspecificF1s and a long-term common garden experiment on the plateau,we provide in situ assessments on 44 growth and physiological traits across four seasons,along with RNA sequencing.We found significantphenotypic divergence between P.densata and its putative parental species P.tabuliformis and P.yunnanensis,with P.densata demonstrating superior growth and dynamic balance between photosynthesis and photoprotection.The F1s closely resembled P.densata in most traits.Gene expression revealed 19%–10%of 34,000 examined genes as differentially expressed in P.densata and F1s relative to mid-parent expression values.Both additive(4%)and non-additive gene actions(5%–6%in F1s,10%–12%in P.densata)were common,while transgressive expression occurred more frequently in the stabilized natural hybrids,illustrating transcriptomic reprogramming brought by hybridization and further divergence by natural selection.We provide compelling evidence for hybridization-derived phenotypic divergence at both physiological and gene expression levels that could have contributed to the adaptation of P.densata to high plateau habitat where both parental species have low fitness.The altered physiology and gene expression in hybrids serve both as a substrate for novel ecological adaptation and as a mechanism for the initiation of reproductive isolation.展开更多
The intergeneric hybridization between Brassica napus L. cv. oro and Matthiola incana (L.) R. Br. was carried out to study the phytogenetic peculiarities of the hybrid plants. In order to improve the oil quality of ra...The intergeneric hybridization between Brassica napus L. cv. oro and Matthiola incana (L.) R. Br. was carried out to study the phytogenetic peculiarities of the hybrid plants. In order to improve the oil quality of rape seed, ovaries of B. napus pollinated with pollen of M. incana, were cut off and inoculated onto MS media supplemented with various plant hormones at the 7th day after pollination. Two mature embryos were obtained from 750 pollinated ovaries cultured in vitro. The percentage of seed set was 0.26%. The mature embryos were transferred onto the MS media supplemented with 2.0 mg/L 6-BA + 0.1 mg/L NAA, and a compound bud was produced later. The compound bud was then cut into a number of single buds, which were transferred onto fresh media. Twenty-two plantlets in vitro were developed from the above single buds. The hybrid plants (F-1) were basically intermediate between the two parents in many,characters with a few showing hybrid vigor. The fertility of hybrid plants (F-1) was poor. Cytological studies revealed that the hybrid plants (F-1) were mixoploid. in nature. The chromosome number of many somatic cells was 2n = 26, which was the sum of the chromosome number of the two parents. The chromosome number of other somatic cells was 2n = 38, similar to that of B. napus. The hybrid offspring (F-2) from the selfed hybrid plants (F-1) showed polymorphism. Among the hybrid offspring (F-2) some were nearly matroclinous and fertile, similar to B. napus. some others were intermediate between the two parents and less fertile, and a few were poorly developed and nearly infertile. From the hybrid offspring a few plants with improved seed-oil quality were obtained.展开更多
To investigate the expression profile of maize genes induced by submergence, a subtracted cDNA library of maize seedling roots was constructed using suppression subtractive hybridization (SSH). The cDNA of maize seedl...To investigate the expression profile of maize genes induced by submergence, a subtracted cDNA library of maize seedling roots was constructed using suppression subtractive hybridization (SSH). The cDNA of maize seedling roots treated with submergence (ST) was used as tester and what from untreated roots (UT) as driver. Products of the secondary PCR from the forward subtraction were cloned into T/A vector and transferred into Escherichia coli strain JM10B by electroporation. Four hundred and eight randomly chosen transformants carrying cDNA fragments were screened with PCR-Select Deferential Screening Kit. One hundred and eighty-four cDNA clones were identified as, submergence specifically induced or highly expressed. After sequencing and removing redundant cDNAs, we got 95 submergence-induced cDNA clones. Of the 95 cDNA clones, 68 contain the regions with 60%-90% identity to their homolog in GenBank, 21 are expected to be novel genes, only 6 correspond to the published maize sequences.展开更多
The technique of producing doublehaploid of wheat by distant hybridization between wheat and maize has characterized with better inducing effect, shorter in- ducing period, easy operation, and so on. At present, it is...The technique of producing doublehaploid of wheat by distant hybridization between wheat and maize has characterized with better inducing effect, shorter in- ducing period, easy operation, and so on. At present, it is the most efficient and has great potential of application in breeding of wheat. This article reviewed princi- ple and production process of the technique, research situation of the three key in- dicators of the technology（embryo rate, seedling rate and success rate of doubling）in recent years, and application of the technology in breeding, genetics, germplasm improvement of wheat. At last, both the achievements and the direction of further improvement and development of the technology in our program were discussed.展开更多
基金the National Natural Science Foundation of China(No.22379069)Fundamental Research Funds for the Central Universities(No.30922010304).
文摘Sluggish sulfur redox kinetics remain a critical bottleneck in the advancement of high-performance lithiumsulfur batteries(LSBs).Single-atom catalysts(SACs)offer a promising solution to this limitation,particularly when their coordination structures are carefully engineered.Here,we develop a chromium-based SAC featuring a unique undercoordinated CrN_(3) configuration to boost sulfur electrochemistry.Compared with conventional CrN_(4),the CrN_(3) motif lowers 3d orbital occupancy and meanwhile activates the in-plane hybridizations with S 3p orbitals upon interaction with polysulfides,contributing to moderate adsorption strength and reduced energy barriers for bidirectional sulfur conversions.Additionally,the integration of the two-dimensional(2D)porous framework ensures abundant electrochemically active surfaces and efficiently exposed active sites.As a result,CrN_(3)-based cells demonstrate fast and durable sulfur redox reactions,enabling an ultralow capacity decay of 0.0075%per cycle over 1000 cycles and a high-rate capability of 651.9 mAh·g^(-1)at 5 C.The CrN_(3) catalyst retains robust catalytic efficiency under demanding conditions,delivering a high areal capacity of 5.53 mAh·cm^(-2) at high sulfur loading and lean electrolyte.This work establishes a compelling paradigm of SAC coordination engineering for designing advanced sulfur electrocatalysts for next-generation LSBs.
基金supported by the Strategic Priority Research Program of Chinese Academy of Sciences (Grant Nos.XDB28000000 and XDB0460000)the Quantum Science and Technology-National Science and Technology Major Project (Grant No.2021ZD0302600)the National Key Research and Development Program of China(Grant No.2024YFA1409002)。
文摘The hybridization gap in strained-layer InAs/In_(x)Ga_(1−x) Sb quantum spin Hall insulators(QSHIs)is significantly enhanced compared to binary InAs/GaSb QSHI structures,where the typical indium composition,x,ranges between 0.2 and 0.4.This enhancement prompts a critical question:to what extent can quantum wells(QWs)be strained while still preserving the fundamental QSHI phase?In this study,we demonstrate the controlled molecular beam epitaxial growth of highly strained-layer QWs with an indium composition of x=0.5.These structures possess a substantial compressive strain within the In_(0.5)Ga_(0.5)Sb QW.Detailed crystal structure analyses confirm the exceptional quality of the resulting epitaxial films,indicating coherent lattice structures and the absence of visible dislocations.Transport measurements further reveal that the QSHI phase in InAs/In_(0.5)Ga_(0.5)Sb QWs is robust and protected by time-reversal symmetry.Notably,the edge states in these systems exhibit giant magnetoresistance when subjected to a modest perpendicular magnetic field.This behavior is in agreement with the𝑍2 topological property predicted by the Bernevig–Hughes–Zhang model,confirming the preservation of topologically protected edge transport in the presence of enhanced bulk strain.
基金supported by the National Key R&D Program of China(Grant No.2022YFA1402902)the National Natural Science Foundation of China(Grant Nos.12374179,12074119,12374145,051B22001,12104157,12134003,and 12304218)the Shanghai Pujiang Program(Grant No.23PJ1402200).
文摘The hybridization between oxygen 2p and transition-metal 3d states largely determines the electronic structure near the Fermi level and related functionalities of transition-metal oxides(TMOs).Considerable efforts have been made to manipulate the p-d hybridization in TMOs by tailoring the spatial orbital overlap via structural engineering.Here,we demonstrate enhanced p-d hybridization in Ba^(2+)-doped LaNiO_(3)epitaxial films by simultaneously modifying both the spatial and energetic overlaps between the O-2p and Ni-3d orbitals.Combining x-ray absorption spectroscopy and firstprinciples calculations,we reveal that the enhanced hybridization stems from the synergistic effects of a reduced chargetransfer energy due to hole injection and an increased spatial orbital overlap due to straightening of Ni-O-Ni bonds.We further show that the enhanced p-d hybridization can be utilized to promote the oxygen evolution activity of LaNiO_(3).This work sheds new insights into the fine-tuning of the electronic structures of TMOs for enhanced functionalities.
基金supported by Guangzhou Development Zone Science and Technology(2021GH10,2020GH10,2023GH02)the University of Macao(MYRG2022-00271-FST)The Science and Technology Development Fund(FDCT)of Macao(0032/2022/A).
文摘Introduction Early cancer detection represents a critical evolution in healthcare,addressing a significant pain point in cancer treatment:the tendency for diagnoses to occur at advanced stages.Traditionally,many cancers are not identified until they have progressed to late stages,where treatment options become limited,less effective,and more costly.This late detection results in poorer prognoses,higher mortality rates,and increased healthcare costs.Without early detection tools like Fluorescence In Situ Hybridization(FISH),these challenges persist,leaving patients with fewer opportunities for successful outcomes.
基金supported by the National Natural Science Foundation of China(No.32161143024,31970405)Iran National Science Foundation,Iran-China(INSF-NSFC)joint project(No.4002006).
文摘The biological species concept defines species as groups of actually or potentially interbreeding natural populations that are reproductively isolated from other such groups(Mayr,1942).Reproductive isolation,whether prezygotic or postzygotic,plays a central role in maintaining species boundaries.However,hybridization between closely related taxa can challenge these boundaries and provide insight into speciation,gene flow,and evolutionary processes(Coyne and Orr,2004).
文摘Photocatalytic hydrogen(H_(2))production using solar energy is a cutting-edge green technology that holds great potential for addressing the urgent fuel and environmental crises[1–3].To achieve high-efficiency H_(2) production,cocatalyst modification is commonly employed to provide active sites for the hydrogen evolution reaction(HER)[4,5].In this context,the kinetics of hydrogen adsorption and desorption at these active sites play a crucial role in enhancing overall photocatalytic H_(2) production efficiency.However,the H adsorption/desorption kinetics often exhibit a trade-off,presenting a significant challenge in achieving an optimal equilibrium between Hads and Hdes in many cocatalyst systems.Therefore,fine-tuning the active sites to optimize the H_(2) evolution kinetics is essential for improving photocatalytic activity[6].
基金financial support of the National Natural Science Foundation of China (22379063)
文摘Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.Herein,we find that oxygen vacancies can significantly boost the capacity,electrochemical kinetics,and structure stability of LDHs.The corresponding structure-performance relationship and energy storage mechanism are elaborated through exhaustive in/ex-situ experimental characterizations and density functional theory(DFT)calculations.Specially,in-situ Raman and DFT calculations reveal that oxygen vacancies elevate orbital energy of O 2p and electron density of O atoms,thereby enhancing the orbital hybridization of O 2p with Ni/Co 3d.This facilitates electron transfer between O and adjacent Ni/Co atoms and improves the covalency of Ni–O and Co–O bonds,which activates Ni/Co atoms to release more capacity and stabilizes the Ov-NiCo-LDH structure.Moreover,the distribution of relaxation times(DRT)and molecular dynamics(MD)simulations disclose that the enhanced d-p orbital hybridization optimizes the electronic structure of Ov-NiCo-LDH,which distinctly reduces the diffusion energy barriers of Mg^(2+)and improves the charge transfer kinetics of Ov-NiCo-LDH.Consequently,the assembled Ov-NiCo-LDH//active carbon(AC)and Ov-NiCo-LDH//perylenediimide(PTCDI)AMIBs can both deliver high specific discharge capacity(182.7 and 59.4 mAh g^(−1)at 0.5 A g^(−1),respectively)and long-term cycling stability(85.4%and 89.0%of capacity retentions after 2500 and 2400 cycles at 1.0 A g^(−1),respectively).In addition,the practical prospects for Ov-NiCo-LDH-based AMIBs have been demonstrated in different application scenarios.This work not only provides an effective strategy for obtaining high-performance cathodes of AMIBs,but also fundamentally elucidates the inherent mechanisms.
基金financially supported by National Natural Science Foundation of China(No.52473327,51572295,21273285 and 21003157)National Key R&D Program of China(No.2021YFA1501300,2019YFC1907602).
文摘Defect engineering significantly enhances electrocatalytic performance by modulating electronic structures and interfacial coordination,yet the dynamic correlation between defect evolution and catalytic activity during reactions remains unclear.Herein,density functional theory(DFT)calculations first reveal the modulation of sulfur vacancy concentrations on Co_(9)S_(8)electronic structures,predicting that optimized vacancy concentrations enable highly efficient electrocatalytic water splitting.Experimentally fabricated Co_(9)S_(8)with appropriate sulfur vacancies exhibits superior bifunctional activity(HER:164 mV@_(η10);OER:297 mV@_(η100)).The MCS-assembled overall water splitting system demonstrates stable operation at 1.57 V(10 mA cm^(−2))for over 60 h.Experimental studies illustrate that sulfur vacancies preferentially adsorb OH^(−)during reactions,inducing the formation of CoOOH active phases.DFT analysis further indicates that OH^(−)adsorption weakens d-p orbital hybridization,optimizing hydrogen/oxygen intermediate adsorption energy barriers and ultimately enhancing catalytic performance.This work establishes novel paradigms for systematic development of catalysts through synergistic analysis of defect dynamics,electronic structures and catalytic performance.
文摘Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains unclear.Additionally,the modulation of reactive oxygen species in Fenton-like reactions remains challenging.Herein,a novel strategy is reported for the rational design of highly loaded Co ASACs(CoN_(1)C_(2)/C_(2)N)immobilized on three-dimensional flower-like C_(2)N using an in situ-generated carbon defect method.In particular,the asymmetrically tricoordinated CoN_(1)C_(2)/C_(2)N exhibited excellent catalytic activity for sulfachloropyridazine degradation,with a turnover frequency of 36.8 min^(–1).Experimental results and theoretical calculations revealed that the electron spin state of the Co-active sites was transferred from the low-spin configuration(t_(2g)^(6)e_(g)^(1))to the high-spin configuration(t_(2g)^(5)e_(g)^(2))owing to asymmetric coordination.The high-spin Co 3d orbital in CoN_(1)C_(2)/C_(2)N possessed more unpaired electrons and therefore,had a strong ability to gain electrons from the O 2p orbitals of HSO_(5)^(–),boosting d-p orbital hybridization.More importantly,the spin-electron filling in theσ^(*)orbital of high-spin Co 3d−O 2p accelerated the desorption of^(*)SO_(5)•^(−),which acted as a rate-limiting step in the reaction,thus facilitating more^(1)O_(2)generation.This study provides an innovative synthetic route for practical ASACs and clarifies the critical relationship between structure and spin state,paving the way for advancements in environmental remediation and energy conversion applications.
基金supported by the National Natural Science Foundation of China(32171816)T4F program Sweden.
文摘Hybridization is a driving force in ecological transitions and speciation,yet direct evidence linking it to adaptive differentiation in natural systems remains limited.This study evaluates the role of hybridization in the speciation of Pinus densata,a keystone forest species on the southeastern Tibetan Plateau.By creating artificialinterspecificF1s and a long-term common garden experiment on the plateau,we provide in situ assessments on 44 growth and physiological traits across four seasons,along with RNA sequencing.We found significantphenotypic divergence between P.densata and its putative parental species P.tabuliformis and P.yunnanensis,with P.densata demonstrating superior growth and dynamic balance between photosynthesis and photoprotection.The F1s closely resembled P.densata in most traits.Gene expression revealed 19%–10%of 34,000 examined genes as differentially expressed in P.densata and F1s relative to mid-parent expression values.Both additive(4%)and non-additive gene actions(5%–6%in F1s,10%–12%in P.densata)were common,while transgressive expression occurred more frequently in the stabilized natural hybrids,illustrating transcriptomic reprogramming brought by hybridization and further divergence by natural selection.We provide compelling evidence for hybridization-derived phenotypic divergence at both physiological and gene expression levels that could have contributed to the adaptation of P.densata to high plateau habitat where both parental species have low fitness.The altered physiology and gene expression in hybrids serve both as a substrate for novel ecological adaptation and as a mechanism for the initiation of reproductive isolation.
文摘The intergeneric hybridization between Brassica napus L. cv. oro and Matthiola incana (L.) R. Br. was carried out to study the phytogenetic peculiarities of the hybrid plants. In order to improve the oil quality of rape seed, ovaries of B. napus pollinated with pollen of M. incana, were cut off and inoculated onto MS media supplemented with various plant hormones at the 7th day after pollination. Two mature embryos were obtained from 750 pollinated ovaries cultured in vitro. The percentage of seed set was 0.26%. The mature embryos were transferred onto the MS media supplemented with 2.0 mg/L 6-BA + 0.1 mg/L NAA, and a compound bud was produced later. The compound bud was then cut into a number of single buds, which were transferred onto fresh media. Twenty-two plantlets in vitro were developed from the above single buds. The hybrid plants (F-1) were basically intermediate between the two parents in many,characters with a few showing hybrid vigor. The fertility of hybrid plants (F-1) was poor. Cytological studies revealed that the hybrid plants (F-1) were mixoploid. in nature. The chromosome number of many somatic cells was 2n = 26, which was the sum of the chromosome number of the two parents. The chromosome number of other somatic cells was 2n = 38, similar to that of B. napus. The hybrid offspring (F-2) from the selfed hybrid plants (F-1) showed polymorphism. Among the hybrid offspring (F-2) some were nearly matroclinous and fertile, similar to B. napus. some others were intermediate between the two parents and less fertile, and a few were poorly developed and nearly infertile. From the hybrid offspring a few plants with improved seed-oil quality were obtained.
文摘To investigate the expression profile of maize genes induced by submergence, a subtracted cDNA library of maize seedling roots was constructed using suppression subtractive hybridization (SSH). The cDNA of maize seedling roots treated with submergence (ST) was used as tester and what from untreated roots (UT) as driver. Products of the secondary PCR from the forward subtraction were cloned into T/A vector and transferred into Escherichia coli strain JM10B by electroporation. Four hundred and eight randomly chosen transformants carrying cDNA fragments were screened with PCR-Select Deferential Screening Kit. One hundred and eighty-four cDNA clones were identified as, submergence specifically induced or highly expressed. After sequencing and removing redundant cDNAs, we got 95 submergence-induced cDNA clones. Of the 95 cDNA clones, 68 contain the regions with 60%-90% identity to their homolog in GenBank, 21 are expected to be novel genes, only 6 correspond to the published maize sequences.
文摘The technique of producing doublehaploid of wheat by distant hybridization between wheat and maize has characterized with better inducing effect, shorter in- ducing period, easy operation, and so on. At present, it is the most efficient and has great potential of application in breeding of wheat. This article reviewed princi- ple and production process of the technique, research situation of the three key in- dicators of the technology（embryo rate, seedling rate and success rate of doubling）in recent years, and application of the technology in breeding, genetics, germplasm improvement of wheat. At last, both the achievements and the direction of further improvement and development of the technology in our program were discussed.
